CA1061050A - Process of preparing polyolefins - Google Patents
Process of preparing polyolefinsInfo
- Publication number
- CA1061050A CA1061050A CA231,566A CA231566A CA1061050A CA 1061050 A CA1061050 A CA 1061050A CA 231566 A CA231566 A CA 231566A CA 1061050 A CA1061050 A CA 1061050A
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- CA
- Canada
- Prior art keywords
- titanium
- carrier
- catalyst
- vanadium
- trichloride
- Prior art date
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- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/08—Butenes
- C08F10/10—Isobutene
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
ABSTRACT OF The DISCLOSURE
A process of polymerizing or copolymerizing a class of olefins is carried out in the presence of a catalyst, which catalyst comprises one of more solid compounds selected as a carrier from the group consist-ing of an oxide, a double oxide and a hydroxide of halogen-free magnesium and/or calcium. The carrier is treated by direct contact with gaseous sulfur dioxide (SO2) under a gaseous atmosphere. A titanium and/or vanadium compound, viz. Ziegler catalyst component, is deposited on the treated carrier and activated by an organometal compound.
A process of polymerizing or copolymerizing a class of olefins is carried out in the presence of a catalyst, which catalyst comprises one of more solid compounds selected as a carrier from the group consist-ing of an oxide, a double oxide and a hydroxide of halogen-free magnesium and/or calcium. The carrier is treated by direct contact with gaseous sulfur dioxide (SO2) under a gaseous atmosphere. A titanium and/or vanadium compound, viz. Ziegler catalyst component, is deposited on the treated carrier and activated by an organometal compound.
Description
~0~105~
This invention relates to a process of preparing polyolefins, and more particularly to the polymerization or copolymerization of olefins using novel catalysts.
Heretofore, there have been proposed a great many catalysts useful for the production of polyolefins. Among such known catalysts are the ones which are obtained by contacting transition metal compounds such as titanium and/or vanadium with organometal compounds of Groups I-IV metals of the Periodic Table. ~n improvement in this type of catalyst is also known which comprises a transition metal compound such as for example titanium tetrachloride supported on an inorganic solid carrier such as magnesium hydroxychloride, magnesium halide, magnesium hydroxide, magnesium oxide or the like and subsequently activated by an organometal compound.
Such supported catalysts are normally very active and in most cases active enough to dispense with the step of catalyst removal which is rather complicated in the process of poly-olefin preparation. For this reason, the recent trend in the art has been directed to the use of magnesium and various other metallic compound carriers for catalyst components.
However, while solid carriers of the type consisting of magnesium hydroxychloride and magnesium halide contribute to increased catalytic activity, they have the drawback that halogen content is relatively high in the polyolefin which is obtained by a process dispensing with the step of catalyst removal. Whereas, another type of carrier consisting of magnesium oxide and magnesium hydroxide is advantageous in respect of the halogen content, but has much to be desired lVSO
for catalytic activity. It is known to improve the activity of magnesium oxide or magnesium hydroxide supported catalysts by halogeneting these magnesium compounds. This however still involves the problem of halogen residues in polymerized products.
Whereas the present invention is aimed at the provi-sion of a process for the polymerization or copol~merization of olefins with use of a novel catalyst capable of giving high yields of polyolefins without involving the foregoing diffi-culties of the prior art.
Briefly stated, there is provided in accordance with the invention a process for the production of polyolefins by polymerizing or copolymerizing one or more olefins in the presence of a catalyst, which catalyst comprises one or more solid compounds selected as a carrier from the group consisting of an oxide, a double oxide and a hydroxide of halogenfree magnesium and/or calcium and pretreated by direct contact with gaseous sulfur dioxide (SO2) under a gaseous atmosphere and a catalyst component consisting of titanium and/or vanadium compound, viz~ Ziegler catalyst component, deposited on said carrier and activated by an organometal compound.
The term gaseous atmosphere as used herein includes an atmosphere of gaseous SO2 alone and an atmosphere of gaseous S2 mixed with an inert gas. By the inert gas is meant a gaseous material which is substantially free from interaction with the above solid carrier when the la~ter is contacted with S2 under conditions hereafter described. Illustrative of such inert gas are air, nitrogen, oxygen and argon.
~.Ot;~ 050 It has now been found that remarkably high catalytic activity in the polymerization or copolymerization of various olefins can be achieved by the use of a catalyst carrier or support consisting of any of the above listed solid compounds which is treated simply by contacting the same with gaseous S2 under a gaseous atmosphere. Catalysts supported on such treated carriers according to the invention exhibit far greater activity particularly based on the transition metal used as compared with catalysts which are not treated with so2.
The term oxide, double oxide and hydroxide of mag-nesium and/or calcium includes any such commercially avail-able products either synthesized or naturally occurring.
The double oxide under contemplation is an oxide of mag-nesium and/or calcium containing one or more of other metals.
Typical examples are MgO A1303, MgO SiO2, MgO A1203 CaO, CaO-A1203, CaO SiO2 and natural or synthetic hydrotalcite.
It is to be noted that these formulae are merely of compo-sition, not of molecular representation and that the struc-ture and the ratio of components of the double oxides employed in the practice of the invention are not to be limited there-by. The oxides, double oxides and hydroxide defined as above may be used alone or as mixtures of two or more of them.
-The solid carriers according to the invention may contain absorbed water if not excessive and may be calcined.
The treatment of the above carrier-forming solid compounds with S02 may be effected by means of a well-known fixed or fluidized bed containing the solid compounds which lO~ilOSO
is brought into direct contact with gaseous SO2 at tempera-tures ranging between room temperature and 800C, preferably between 120C and 300C for a period of 1 to 24 hours, al-though this contact time length is not mandatory. While the precise details of the reaction which takes place of the solid carrier with SO2 are not known, there have been found substantial amounts of sulfur atom in the S02 treated solid compound, which believably accounts for the possibility of forming a novel carrier. The conditions of contact of the solid compound with SO2 should be adjusted so that sulfur content in the treated solid carrier may be in the range of 0.1 to 20 weight percent, preferably 0.5 to 5 weight percent to obtain a maximum catalytic activity.
Any conventional procedure may be employed for sup-porting titanium and/or vanadium compounds on the above carriers. For example, the carrier may be contacted under heated conditions with a transition metal compound of the class hereafter identified either in the presence or in the absence of suitable inert solvents. Conveniently both carrier and transition metal compound may be heated at temperatures ranging between 50 and 300C, preferably between 100 and 150C without solvents. Reaction time is not restricted but may ordinarily be 5 minutes or longer, possible up to 10 hours, although this upper limit is not too important~ An alternative procedure is to bring both materials mechanically into contact with each other as by means of ball milling, which of course should be done in an inert gas atmosphere free of oxygen and moisture.
1061(~S(J
The transition metal compound may be used in amounts of 0.001 to 50 times by weight with respect to the carrier, with excess transition metal compound preferably removed with a solvent after the same has been deposited on the carrier. There is no limitation as to how to remove un-reacted transition metal compound. This can be done by repeatedly washing the compound with a solvent inert to Ziegler catalysts and evaporating the washing liquid under vacuum so as to obtain solid particles as is well known in the art.
The polymerization reaction of olefins using the catalyst of the invention is conducted substantially in the same manner as in the polymerization reaction using a - conventional Ziegler catalyst, wherein substantially oxygen- and moisture-free conditions are maintained throughout the reaction. The polymerization conditions for olefins include a temperature in the range of 20 to 300C, preferably 50 to 180C and a pressure in the range of normal to 70 kg/cm2, preferably 2 to 60 kg/cm2. Mo-lecular weight control may be effected to some degree by changing the polymerization conditions such as temperatures and mol ratio of the catalyst but can be more effectively done by addition of hydrogen to the polymerization system.
With the catalyst of the invention, two- or more multi-stage reactions can be effected under different hydrogen concentrat~ons, temperatures and other polymerization conditions.
~0~105~3 The process of the invention can be applied to the polymerization of all olefins polymerizable with Ziegler catalysts and typically to the homopolymerization of alpha-olefins such as ethylene, propylene and l-butene, or to the copolymerization of ethylene and propylene, ethylene and l-butene, and propylene and l-butene.
The transition metal compounds employed in accordance with the invention may be any titanium or vanadium compounds which can be used as Ziegler catalyst components. Illustra-tive are tetravalent titanium compounds such as titanium tetrachloride, titanium tetrabromide, mono-ethoxytitanium trichloride, diethoxytitanium dichloride, dibuthoxytitanium dichloride, phenoxytitanium trichloride and tetra-n-buthoxytitanium; trivalent titanium compounds such as titanium trichloride and titanium trichloride-aluminum trichloride complex; trivalent vanadium compounds such as vanadium trichloride; tetravalent vanadium compounds such as vanadium tetrachloride; and pentavalent vanadium compounds such as vanadium oxytrichloride and orthoalkyl vanadate.
The term organometal compound as used herein includes compounds of metals of Group I-IV of the Periodic table which are generally known as Ziegler catalyst components.
Preferable are organoaluminum compounds and organozinc compounds. The organoaluminum compounds are represented by the general formulae:
RsAl, R2AlX, RAlX2, R2AlOR, RAl(OR~ , RAl(OR)X
and R3A12X3 l~lOSO
wherein R is alkyl or aryl group and X is halogen atom.
The organozinc compounds are represented by the general formula:
wherein R is alkyl group. Typical examples of such organo-metal compounds include triethylaluminum, triisobutyl-aluminum, trihexylaluminum, trioctylaluminum, tridecyl-aluminum, diethylaluminum chloride, ethylaluminum sesqui-chloride, diethylzinc, and mixtures thereof. No particular limitations are imposed upon the amount of each of these organometal compounds to be used in the process of the inYention. However, the organometal compounds can usually be used in amounts of 0.1 to 1,000 mol times the transition matal halide.
The invention will be further described by way of the following examples which are merely illustrative but are not intended to limit the invention thereto.
Example (a) Preparation of Catalyst 10 grams of a commercially available magnesium oxide were heated at 500C for 5 hours. The oxide was thereafter placed in a glass tube 3.5 cm in diameter equipped with a perforated plate and maintained at 200C, while gaseous SO2 was supplied from the lower portion of the tube for a period of 4 hours. After completion of this treatment, a purified nitrogen gas was introduced at 200C for 30 minutes, until there was obtained a carrier having a sulfur content of 3.7 lO~lOSl~
weight percent. The resulting carrier was transferred to a flask equipped with stirrer and containing 80 ml titanium tetrachloride. The admixture was heated at 130C for 2 hours and thereafter washed with hexane. Washing was repeated until the titanium tetrachloride completely dis-appeared. The solid portion of the product was dried and analyzed to show a deposit of 14 mg titanium per gram of solid.
(b) Polymerization A 2 liter stainless steel autoclave equipped with an induction stirrer was purged with nitrogen and charged with 1,000 ml hexane, 5 millimols triethyl aluminum and 612 mg of the solid prepared as above. The whole was heated to 90C with stirring. The system was pressurized to 2 kg/cm2 by the vapor pressure of hexane and charged with hydrogen to a total pressure of 6 kg/cm2, followed by a continuous charge of ethylene to a total pressure of 10 kg/cm2. The polymerization reaction was thus initiated and continued for one hour. After completion of the re-action, the polymer slurry was transferred to a beaker, and hexane was removed under vacuum thereby providing 362 grams white polyethylene having a melt index of 1.78. Catalytic activity was represented by 10,600 grams polyethylene per gram titanium per hour per ethylene pressure, or 148 grams polyethylene per gram solid per hour per ethylene pressure.
This value of catalytic activity per titanium is far greater than that obtainable with the catalyst which is not pre-~0~;1050 treated with SO2 as in Comparing Example 1 below.
Comparing Example The precedure of Example 1 was followed in the preparation of a catalyst except that magnesium oxide was not treated with SO2. The resulting catalyst had a deposit of 60 mg titanium per gram solid. 161 mg of this catalyst were used in the polymerization of ethylene which was ef-fected under the same conditions as in Example 1. There was obtained 101 grams white polyethylene having a melt index of 1.37. Catalytic activity was represented by
This invention relates to a process of preparing polyolefins, and more particularly to the polymerization or copolymerization of olefins using novel catalysts.
Heretofore, there have been proposed a great many catalysts useful for the production of polyolefins. Among such known catalysts are the ones which are obtained by contacting transition metal compounds such as titanium and/or vanadium with organometal compounds of Groups I-IV metals of the Periodic Table. ~n improvement in this type of catalyst is also known which comprises a transition metal compound such as for example titanium tetrachloride supported on an inorganic solid carrier such as magnesium hydroxychloride, magnesium halide, magnesium hydroxide, magnesium oxide or the like and subsequently activated by an organometal compound.
Such supported catalysts are normally very active and in most cases active enough to dispense with the step of catalyst removal which is rather complicated in the process of poly-olefin preparation. For this reason, the recent trend in the art has been directed to the use of magnesium and various other metallic compound carriers for catalyst components.
However, while solid carriers of the type consisting of magnesium hydroxychloride and magnesium halide contribute to increased catalytic activity, they have the drawback that halogen content is relatively high in the polyolefin which is obtained by a process dispensing with the step of catalyst removal. Whereas, another type of carrier consisting of magnesium oxide and magnesium hydroxide is advantageous in respect of the halogen content, but has much to be desired lVSO
for catalytic activity. It is known to improve the activity of magnesium oxide or magnesium hydroxide supported catalysts by halogeneting these magnesium compounds. This however still involves the problem of halogen residues in polymerized products.
Whereas the present invention is aimed at the provi-sion of a process for the polymerization or copol~merization of olefins with use of a novel catalyst capable of giving high yields of polyolefins without involving the foregoing diffi-culties of the prior art.
Briefly stated, there is provided in accordance with the invention a process for the production of polyolefins by polymerizing or copolymerizing one or more olefins in the presence of a catalyst, which catalyst comprises one or more solid compounds selected as a carrier from the group consisting of an oxide, a double oxide and a hydroxide of halogenfree magnesium and/or calcium and pretreated by direct contact with gaseous sulfur dioxide (SO2) under a gaseous atmosphere and a catalyst component consisting of titanium and/or vanadium compound, viz~ Ziegler catalyst component, deposited on said carrier and activated by an organometal compound.
The term gaseous atmosphere as used herein includes an atmosphere of gaseous SO2 alone and an atmosphere of gaseous S2 mixed with an inert gas. By the inert gas is meant a gaseous material which is substantially free from interaction with the above solid carrier when the la~ter is contacted with S2 under conditions hereafter described. Illustrative of such inert gas are air, nitrogen, oxygen and argon.
~.Ot;~ 050 It has now been found that remarkably high catalytic activity in the polymerization or copolymerization of various olefins can be achieved by the use of a catalyst carrier or support consisting of any of the above listed solid compounds which is treated simply by contacting the same with gaseous S2 under a gaseous atmosphere. Catalysts supported on such treated carriers according to the invention exhibit far greater activity particularly based on the transition metal used as compared with catalysts which are not treated with so2.
The term oxide, double oxide and hydroxide of mag-nesium and/or calcium includes any such commercially avail-able products either synthesized or naturally occurring.
The double oxide under contemplation is an oxide of mag-nesium and/or calcium containing one or more of other metals.
Typical examples are MgO A1303, MgO SiO2, MgO A1203 CaO, CaO-A1203, CaO SiO2 and natural or synthetic hydrotalcite.
It is to be noted that these formulae are merely of compo-sition, not of molecular representation and that the struc-ture and the ratio of components of the double oxides employed in the practice of the invention are not to be limited there-by. The oxides, double oxides and hydroxide defined as above may be used alone or as mixtures of two or more of them.
-The solid carriers according to the invention may contain absorbed water if not excessive and may be calcined.
The treatment of the above carrier-forming solid compounds with S02 may be effected by means of a well-known fixed or fluidized bed containing the solid compounds which lO~ilOSO
is brought into direct contact with gaseous SO2 at tempera-tures ranging between room temperature and 800C, preferably between 120C and 300C for a period of 1 to 24 hours, al-though this contact time length is not mandatory. While the precise details of the reaction which takes place of the solid carrier with SO2 are not known, there have been found substantial amounts of sulfur atom in the S02 treated solid compound, which believably accounts for the possibility of forming a novel carrier. The conditions of contact of the solid compound with SO2 should be adjusted so that sulfur content in the treated solid carrier may be in the range of 0.1 to 20 weight percent, preferably 0.5 to 5 weight percent to obtain a maximum catalytic activity.
Any conventional procedure may be employed for sup-porting titanium and/or vanadium compounds on the above carriers. For example, the carrier may be contacted under heated conditions with a transition metal compound of the class hereafter identified either in the presence or in the absence of suitable inert solvents. Conveniently both carrier and transition metal compound may be heated at temperatures ranging between 50 and 300C, preferably between 100 and 150C without solvents. Reaction time is not restricted but may ordinarily be 5 minutes or longer, possible up to 10 hours, although this upper limit is not too important~ An alternative procedure is to bring both materials mechanically into contact with each other as by means of ball milling, which of course should be done in an inert gas atmosphere free of oxygen and moisture.
1061(~S(J
The transition metal compound may be used in amounts of 0.001 to 50 times by weight with respect to the carrier, with excess transition metal compound preferably removed with a solvent after the same has been deposited on the carrier. There is no limitation as to how to remove un-reacted transition metal compound. This can be done by repeatedly washing the compound with a solvent inert to Ziegler catalysts and evaporating the washing liquid under vacuum so as to obtain solid particles as is well known in the art.
The polymerization reaction of olefins using the catalyst of the invention is conducted substantially in the same manner as in the polymerization reaction using a - conventional Ziegler catalyst, wherein substantially oxygen- and moisture-free conditions are maintained throughout the reaction. The polymerization conditions for olefins include a temperature in the range of 20 to 300C, preferably 50 to 180C and a pressure in the range of normal to 70 kg/cm2, preferably 2 to 60 kg/cm2. Mo-lecular weight control may be effected to some degree by changing the polymerization conditions such as temperatures and mol ratio of the catalyst but can be more effectively done by addition of hydrogen to the polymerization system.
With the catalyst of the invention, two- or more multi-stage reactions can be effected under different hydrogen concentrat~ons, temperatures and other polymerization conditions.
~0~105~3 The process of the invention can be applied to the polymerization of all olefins polymerizable with Ziegler catalysts and typically to the homopolymerization of alpha-olefins such as ethylene, propylene and l-butene, or to the copolymerization of ethylene and propylene, ethylene and l-butene, and propylene and l-butene.
The transition metal compounds employed in accordance with the invention may be any titanium or vanadium compounds which can be used as Ziegler catalyst components. Illustra-tive are tetravalent titanium compounds such as titanium tetrachloride, titanium tetrabromide, mono-ethoxytitanium trichloride, diethoxytitanium dichloride, dibuthoxytitanium dichloride, phenoxytitanium trichloride and tetra-n-buthoxytitanium; trivalent titanium compounds such as titanium trichloride and titanium trichloride-aluminum trichloride complex; trivalent vanadium compounds such as vanadium trichloride; tetravalent vanadium compounds such as vanadium tetrachloride; and pentavalent vanadium compounds such as vanadium oxytrichloride and orthoalkyl vanadate.
The term organometal compound as used herein includes compounds of metals of Group I-IV of the Periodic table which are generally known as Ziegler catalyst components.
Preferable are organoaluminum compounds and organozinc compounds. The organoaluminum compounds are represented by the general formulae:
RsAl, R2AlX, RAlX2, R2AlOR, RAl(OR~ , RAl(OR)X
and R3A12X3 l~lOSO
wherein R is alkyl or aryl group and X is halogen atom.
The organozinc compounds are represented by the general formula:
wherein R is alkyl group. Typical examples of such organo-metal compounds include triethylaluminum, triisobutyl-aluminum, trihexylaluminum, trioctylaluminum, tridecyl-aluminum, diethylaluminum chloride, ethylaluminum sesqui-chloride, diethylzinc, and mixtures thereof. No particular limitations are imposed upon the amount of each of these organometal compounds to be used in the process of the inYention. However, the organometal compounds can usually be used in amounts of 0.1 to 1,000 mol times the transition matal halide.
The invention will be further described by way of the following examples which are merely illustrative but are not intended to limit the invention thereto.
Example (a) Preparation of Catalyst 10 grams of a commercially available magnesium oxide were heated at 500C for 5 hours. The oxide was thereafter placed in a glass tube 3.5 cm in diameter equipped with a perforated plate and maintained at 200C, while gaseous SO2 was supplied from the lower portion of the tube for a period of 4 hours. After completion of this treatment, a purified nitrogen gas was introduced at 200C for 30 minutes, until there was obtained a carrier having a sulfur content of 3.7 lO~lOSl~
weight percent. The resulting carrier was transferred to a flask equipped with stirrer and containing 80 ml titanium tetrachloride. The admixture was heated at 130C for 2 hours and thereafter washed with hexane. Washing was repeated until the titanium tetrachloride completely dis-appeared. The solid portion of the product was dried and analyzed to show a deposit of 14 mg titanium per gram of solid.
(b) Polymerization A 2 liter stainless steel autoclave equipped with an induction stirrer was purged with nitrogen and charged with 1,000 ml hexane, 5 millimols triethyl aluminum and 612 mg of the solid prepared as above. The whole was heated to 90C with stirring. The system was pressurized to 2 kg/cm2 by the vapor pressure of hexane and charged with hydrogen to a total pressure of 6 kg/cm2, followed by a continuous charge of ethylene to a total pressure of 10 kg/cm2. The polymerization reaction was thus initiated and continued for one hour. After completion of the re-action, the polymer slurry was transferred to a beaker, and hexane was removed under vacuum thereby providing 362 grams white polyethylene having a melt index of 1.78. Catalytic activity was represented by 10,600 grams polyethylene per gram titanium per hour per ethylene pressure, or 148 grams polyethylene per gram solid per hour per ethylene pressure.
This value of catalytic activity per titanium is far greater than that obtainable with the catalyst which is not pre-~0~;1050 treated with SO2 as in Comparing Example 1 below.
Comparing Example The precedure of Example 1 was followed in the preparation of a catalyst except that magnesium oxide was not treated with SO2. The resulting catalyst had a deposit of 60 mg titanium per gram solid. 161 mg of this catalyst were used in the polymerization of ethylene which was ef-fected under the same conditions as in Example 1. There was obtained 101 grams white polyethylene having a melt index of 1.37. Catalytic activity was represented by
2,620 grams polyethylene per gram titanium per hour per ethylene pressure.
Example 2 The procedure of Example 1 was followed in the preparation of catalyst except that magnesium oxide was treated with SO2 at 100C for 3 hours, thereby providing a carrier having a sulfur content of 3.2 weight percent.
Titanium tetrachloride was deposited on the carrier under the same conditions as in Example 1. The resulting catalyst had a deposit of 21 mg titanium per gram solid.
Ethylene was polymerized with use of 320 mg of cata-lyst according to the procedure of Example 1. There was obtained 190 grams white polyethylene having a melt index of 1.42. Catalytic activity was represented by 7,050 grams polyethylene per gram titanium per hour per ethylene pres-sure.
:10610S~
Example 3 The precedure of Example 1 was followed in the preparation of catalyst except that 10 grams magnesium hydroxide was used. 2 mg titanium was deposited per gram solid. 3,720 mg of this catalyst were used in the poly-merization of ethylene conducted under the same conditions as in Example 1. There was obtained 200 grams white poly-ethylene having a melt index of 0.63. Catalytic activity was represented by 6,700 grams polyethylene per gram tita-nium per hour per ethylene pressure.
Comparing Example 2 The procedure of Example 3 was followed in the preparation of catalyst except that magnesium hydroxide was not treated with SO2. 10 mg titanium was deposited per gram solid. 1,180 mg of this catalyst were used in the polymerization of ethylene conducted in accordance with the procedure of Example 1. There was obtained 187 grams white polyethylene having a melt index of 0.14. Catalytic 2~ activity was 3,900 grams polyethylene per gram titanium per hour per ethylene pressure.
Example 4 A commercially available MgO-A12O3 (Mg/Al atomic ratio = 1.25) was heated at 500C for 5 hours and treated with SO2 at 200!C for 5 hours, until there was obtained a carrier having a sulfur content of 3.5 weight percent.. A
catalyst was prepared using this carrier in the same manner ~0~10~
as in Example 1. The catalyst had a deposit of 18 mg tita-nium per gram solid. The procedure of Example 1 was also followed in the polymerization of ethylene except that 293 mg of this catalyst were used. There was obtained 46 grams white polyethylene having a melt index of 0.02. Catalytic activity was 2,150 grams polyethylene per gram titanium per hour per ethylene pressure.
Comparing Example 3 The procedure of Example 4 was followed in catalyst preparation except that the carrier was not treated with SO2. Ethylene was polymerized with use of 132 grams of this-catalyst. There was obtained 19 grams polyethylene having a melt index of 0.06. Catalytic activity was 1,030 grams polyethylene per gram titanium per hour per ethylene pressure.
Example 5 The procedure of Example 1 was followed in catalyst preparation except that trichloromonobutoxy titanium was used in place of titanium tetrachloride. The resulting catalyst had a deposit of 13 mg titanium per gram solid.
The procedure of Example 1 was also followed in the poly-merization of ethylene except that 357 mg catalyst and triisobutylaluminum instead of triethylaluminum were used.
There was obtained 184 grams white polyethylene having a melt index of 1.51. Catalytic activity was 9,900 grams polyethylene per gram titanium per hour per ethylene pres-sure.
10~10~
Comparing Example 4 The procedure of Example 5 was followed in catalyst preparation except that the carrier was not treated with SO2.
Ethylene was polymerized with this catalyst under the same conditions as in Example 5. There was obtained 61 grams white polyethylene having a melt index of 1.30. Catalytic activity was 2,710 grams polyethylene per gram titanium per hour per ethylene pressure.
Example 6 581 mg catalyst prepared in Example 1 was used in the polymerization reaction wherein hexane, triethylaluminum, solid catalyst and Aydrogen were charged into the autoclave, followed by a charge of ethylene-propylene gas containing 2 mol percent of propylene at 90C. The reaction was con-tinued for one hour maintaining the autoclave at 10 kg/cm2.
There was obtained 298 grams ethylene-propylene copolymer having a melt index of 1.65 and containing 4.9 methyl groups per 1,000 carbon atoms. Catalytic activity was 9,150 grams polyethylene per gram titanium per hour per ethylene pres-sure.
Example 7 The procedure of Example 1 was followed in catalyst preparation except that vanadium tetrachloride was used in lieu of titanium tetrachloride. There was obtained a cata-lyst having 19 mg vanadium deposited per gram solid. Ethylene was polymerized with use of 398 mg of this catalyst in the same manner as in Example 1. There was obtained 228 grams white polyethylene having a melt index of 1.05. Catalytic activity was 7,520 grams polyethylene per gram vanadium per hour per ethylene pressure.
s Comparing Example 5 The procedure of Comparing Example 1 was followed in catalyst preparation except that vanadium tetrachloride was used in lieu of titanium tetrachloride. Example 1 was followed in the polymerization of ethylene. Catalytic activity was 2,500 grams polyethylene per gram vanadium per hour per ethylene pressure.
Example 8 The procedure of Example 1 was followed in catalyst preparation except that calcium oxide was used in lieu of magnesium oxide. 531 mg of the resulting catalyst were used in the polymerization of ethylene in the same manner as in Example 1. There was obtained 70 grams white poly-ethylene. Catalytic activity was 3,000 grams polyethylene per gram titanium per hour per ethylene pressure.
Comparing Example 6 The procedure of Example 8 was followed in catalyst preparation except that the SO2 treatment was omitted.
Polymerization was carried out in accordance with the pro-cedure of Example 1. Catalytic activity was 938 grams polyethylene per gram titanium per hour per ethylene pres-sure.
Example 2 The procedure of Example 1 was followed in the preparation of catalyst except that magnesium oxide was treated with SO2 at 100C for 3 hours, thereby providing a carrier having a sulfur content of 3.2 weight percent.
Titanium tetrachloride was deposited on the carrier under the same conditions as in Example 1. The resulting catalyst had a deposit of 21 mg titanium per gram solid.
Ethylene was polymerized with use of 320 mg of cata-lyst according to the procedure of Example 1. There was obtained 190 grams white polyethylene having a melt index of 1.42. Catalytic activity was represented by 7,050 grams polyethylene per gram titanium per hour per ethylene pres-sure.
:10610S~
Example 3 The precedure of Example 1 was followed in the preparation of catalyst except that 10 grams magnesium hydroxide was used. 2 mg titanium was deposited per gram solid. 3,720 mg of this catalyst were used in the poly-merization of ethylene conducted under the same conditions as in Example 1. There was obtained 200 grams white poly-ethylene having a melt index of 0.63. Catalytic activity was represented by 6,700 grams polyethylene per gram tita-nium per hour per ethylene pressure.
Comparing Example 2 The procedure of Example 3 was followed in the preparation of catalyst except that magnesium hydroxide was not treated with SO2. 10 mg titanium was deposited per gram solid. 1,180 mg of this catalyst were used in the polymerization of ethylene conducted in accordance with the procedure of Example 1. There was obtained 187 grams white polyethylene having a melt index of 0.14. Catalytic 2~ activity was 3,900 grams polyethylene per gram titanium per hour per ethylene pressure.
Example 4 A commercially available MgO-A12O3 (Mg/Al atomic ratio = 1.25) was heated at 500C for 5 hours and treated with SO2 at 200!C for 5 hours, until there was obtained a carrier having a sulfur content of 3.5 weight percent.. A
catalyst was prepared using this carrier in the same manner ~0~10~
as in Example 1. The catalyst had a deposit of 18 mg tita-nium per gram solid. The procedure of Example 1 was also followed in the polymerization of ethylene except that 293 mg of this catalyst were used. There was obtained 46 grams white polyethylene having a melt index of 0.02. Catalytic activity was 2,150 grams polyethylene per gram titanium per hour per ethylene pressure.
Comparing Example 3 The procedure of Example 4 was followed in catalyst preparation except that the carrier was not treated with SO2. Ethylene was polymerized with use of 132 grams of this-catalyst. There was obtained 19 grams polyethylene having a melt index of 0.06. Catalytic activity was 1,030 grams polyethylene per gram titanium per hour per ethylene pressure.
Example 5 The procedure of Example 1 was followed in catalyst preparation except that trichloromonobutoxy titanium was used in place of titanium tetrachloride. The resulting catalyst had a deposit of 13 mg titanium per gram solid.
The procedure of Example 1 was also followed in the poly-merization of ethylene except that 357 mg catalyst and triisobutylaluminum instead of triethylaluminum were used.
There was obtained 184 grams white polyethylene having a melt index of 1.51. Catalytic activity was 9,900 grams polyethylene per gram titanium per hour per ethylene pres-sure.
10~10~
Comparing Example 4 The procedure of Example 5 was followed in catalyst preparation except that the carrier was not treated with SO2.
Ethylene was polymerized with this catalyst under the same conditions as in Example 5. There was obtained 61 grams white polyethylene having a melt index of 1.30. Catalytic activity was 2,710 grams polyethylene per gram titanium per hour per ethylene pressure.
Example 6 581 mg catalyst prepared in Example 1 was used in the polymerization reaction wherein hexane, triethylaluminum, solid catalyst and Aydrogen were charged into the autoclave, followed by a charge of ethylene-propylene gas containing 2 mol percent of propylene at 90C. The reaction was con-tinued for one hour maintaining the autoclave at 10 kg/cm2.
There was obtained 298 grams ethylene-propylene copolymer having a melt index of 1.65 and containing 4.9 methyl groups per 1,000 carbon atoms. Catalytic activity was 9,150 grams polyethylene per gram titanium per hour per ethylene pres-sure.
Example 7 The procedure of Example 1 was followed in catalyst preparation except that vanadium tetrachloride was used in lieu of titanium tetrachloride. There was obtained a cata-lyst having 19 mg vanadium deposited per gram solid. Ethylene was polymerized with use of 398 mg of this catalyst in the same manner as in Example 1. There was obtained 228 grams white polyethylene having a melt index of 1.05. Catalytic activity was 7,520 grams polyethylene per gram vanadium per hour per ethylene pressure.
s Comparing Example 5 The procedure of Comparing Example 1 was followed in catalyst preparation except that vanadium tetrachloride was used in lieu of titanium tetrachloride. Example 1 was followed in the polymerization of ethylene. Catalytic activity was 2,500 grams polyethylene per gram vanadium per hour per ethylene pressure.
Example 8 The procedure of Example 1 was followed in catalyst preparation except that calcium oxide was used in lieu of magnesium oxide. 531 mg of the resulting catalyst were used in the polymerization of ethylene in the same manner as in Example 1. There was obtained 70 grams white poly-ethylene. Catalytic activity was 3,000 grams polyethylene per gram titanium per hour per ethylene pressure.
Comparing Example 6 The procedure of Example 8 was followed in catalyst preparation except that the SO2 treatment was omitted.
Polymerization was carried out in accordance with the pro-cedure of Example 1. Catalytic activity was 938 grams polyethylene per gram titanium per hour per ethylene pres-sure.
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the production of polyolefins by poly-merizing or copolymerizing one or more olefins in the presence of a catalyst, which catalyst comprises one or more solid compounds selected as a carrier from the group consisting of an oxide, a double oxide and a hydroxide of magnesium and/or calcium, said carrier being pretreated by direct contact with gaseous sulfur dioxide (SO2) under a gaseous atmosphere, and a catalyst component consisting of a titanium and/or a vanadium compound deposited on said carrier and activated by an organo-metal compound.
2. The process of claim 1 wherein said carrier is con-tacted with SO2 at a temperature in the range of room tempera-ture to 800°C.
3. The process of claim 1 wherein the SO2 treated carrier contains a sulfur content of 0.1 to 20 weight percent.
4. The process of claim 1 wherein said double oxide is selected from the group consisting of MgO.A13O3, MgO.SiO2, MgO.A12O3.CaO,CaO.A12O3, CaO.SiO2 and natural or synthetic hydrotalcite.
5. The process of claim 1 wherein said carrier is contacted with said catalyst component at a temperature in the range of 50°C to 300°C.
6. The process of claim 1 wherein said catalyst component is used in amounts of 0.001 to SO times by weight with respect to said carrier.
7. The process of claim 1, 2 or 3 wherein the titanium and/or vanadium compounds are chosen from the group consisting of tetravalent titanium compounds chosen from titanium tetrachloride, titanium tetrabromide, mono-ethoxy-titanium trichloride, diethoxytitanium dichloride, dibuthoxy-titanium dichloride, phenoxytitanium trichloride and tetra-n-buthoxytitanium; trivalent titanium compounds chosen from titanium trichloride and titanium trichloride-aluminum trichloride complex; trivalent vanadium compounds chosen from vanadium trichloride; tetravalent vanadium compounds chosen from vanadium tetrachloride; and pentaualent vanadium compounds chosen from vanadium oxytrichloride and orthoalkyl vanadate.
8. The process of claim 1, 2 or 3 wherein the one or more olefins are selected from the group consisting of ethylene, propylene and l-butene.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP49082119A JPS5111879A (en) | 1974-07-19 | 1974-07-19 | Horiorefuinno seizohoho |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1061050A true CA1061050A (en) | 1979-08-21 |
Family
ID=13765513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA231,566A Expired CA1061050A (en) | 1974-07-19 | 1975-07-15 | Process of preparing polyolefins |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4027088A (en) |
| JP (1) | JPS5111879A (en) |
| BR (1) | BR7504615A (en) |
| CA (1) | CA1061050A (en) |
| DE (1) | DE2531899A1 (en) |
| FR (1) | FR2278710A1 (en) |
| IT (1) | IT1041312B (en) |
| ZA (1) | ZA754582B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1553673A (en) * | 1975-07-30 | 1979-09-26 | Bp Chem Int Ltd | Polymerisation catalyst |
| USRE31443E (en) * | 1977-12-05 | 1983-11-15 | Phillips Petroleum Company | Treatment of silica |
| US4248735A (en) * | 1979-06-01 | 1981-02-03 | Phillips Petroleum Company | Treatment of silica |
| USRE31390E (en) * | 1977-12-05 | 1983-09-20 | Phillips Petroleum Company | Treatment of silica |
| DK494578A (en) * | 1977-12-05 | 1979-06-06 | Phillips Petroleum Co | PROCEDURE FOR PREPARING AN OLEPHINE POLYMERIZATION CATALYST |
| JPS6033015Y2 (en) * | 1978-04-28 | 1985-10-02 | 株式会社学習研究社 | Rotary multicolor printer |
| NL7900759A (en) * | 1979-01-31 | 1980-08-04 | Markus Hermetische Deuren | SILL ASSEMBLY. |
| US4277370A (en) * | 1979-02-15 | 1981-07-07 | Standard Oil Company (Indiana) | Alpha-olefin polymerization catalyst |
| US4324690A (en) * | 1979-02-15 | 1982-04-13 | Standard Oil Company (Indiana) | Alpha-olefin polymerization catalyst |
| US4297460A (en) * | 1979-06-01 | 1981-10-27 | Phillips Petroleum Co. | Treatment of silica |
| JPH0420452Y2 (en) * | 1985-12-13 | 1992-05-11 | ||
| CN111072797B (en) * | 2018-10-19 | 2021-07-02 | 中国石油化工股份有限公司 | Olefin polymerization catalyst spherical carrier and preparation method thereof, catalyst component, catalyst and application |
| CN111848845B (en) * | 2020-07-03 | 2023-03-24 | 江苏扬农化工集团有限公司 | Catalyst for preparing low-entanglement ultrahigh molecular weight polyethylene and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2345655A (en) * | 1940-03-23 | 1944-04-04 | Idaho Maryland Mines Corp | Process for producing magnesium sulphate from magnesium-bearing rocks |
| CA936545A (en) * | 1969-11-29 | 1973-11-06 | Distugil | Procede et appareil perfectionnes pour la preparation de dichlorobutenes par chlorination du butadiene |
-
1974
- 1974-07-19 JP JP49082119A patent/JPS5111879A/en active Granted
-
1975
- 1975-07-11 US US05/595,371 patent/US4027088A/en not_active Expired - Lifetime
- 1975-07-15 CA CA231,566A patent/CA1061050A/en not_active Expired
- 1975-07-16 ZA ZA00754582A patent/ZA754582B/en unknown
- 1975-07-17 DE DE19752531899 patent/DE2531899A1/en not_active Withdrawn
- 1975-07-18 FR FR7522587A patent/FR2278710A1/en active Granted
- 1975-07-18 BR BR7504615*A patent/BR7504615A/en unknown
- 1975-07-18 IT IT68888/75A patent/IT1041312B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| FR2278710A1 (en) | 1976-02-13 |
| IT1041312B (en) | 1980-01-10 |
| BR7504615A (en) | 1976-07-06 |
| JPS5248913B2 (en) | 1977-12-13 |
| JPS5111879A (en) | 1976-01-30 |
| ZA754582B (en) | 1976-07-28 |
| US4027088A (en) | 1977-05-31 |
| FR2278710B1 (en) | 1980-11-07 |
| DE2531899A1 (en) | 1976-02-05 |
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